CN114539291A - Intrinsic quinoid near-infrared receptor micromolecules and preparation method and application thereof - Google Patents

Intrinsic quinoid near-infrared receptor micromolecules and preparation method and application thereof Download PDF

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CN114539291A
CN114539291A CN202210038930.0A CN202210038930A CN114539291A CN 114539291 A CN114539291 A CN 114539291A CN 202210038930 A CN202210038930 A CN 202210038930A CN 114539291 A CN114539291 A CN 114539291A
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段春晖
杨明群
曹镛
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South China University of Technology SCUT
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Abstract

The invention relates to an intrinsic quinoid near-infrared receptor micromolecule, which has the following structure:
Figure DDA0003469416740000011
wherein n is a positive integer selected from 1 to 3; q is a quinoid unit, D is an electron donor, and A is an electron acceptor. The structure of the intrinsic quinoid near-infrared receptor micromolecule provided by the invention can effectively improve the quinoid content of a conjugated framework and promote the delocalization of electron cloud on the conjugated framework, thereby expanding the photoresponse range to a near-infrared band; the method is applied to the field of organic photodetectors, and has high responsivity and detectivity at 1100nm, larger cut-off bandwidth and wide linear dynamic range. The preparation method provided by the invention has the advantages of simple process, high yield and structure adjustmentFlexibility, low manufacturing cost, suitability for industrial production and the like.

Description

Intrinsic quinoid near-infrared receptor micromolecules and preparation method and application thereof
Technical Field
The invention relates to the field of organic photoelectricity, in particular to an intrinsic quinoid near-infrared receptor micromolecule and a preparation method and application thereof.
Background
Organic Photodetectors (OPDs) are organic photoelectric devices having a photoelectric conversion function, which can convert incident light into an electrical signal to be output. Compared with the traditional inorganic semiconductor photoelectric detector, the OPDs have the advantages of low cost, low power consumption, capability of realizing solution processing, preparation of flexible devices and the like. Meanwhile, due to the active layer materials with various molecular structures, the detection range can be covered from an ultraviolet light wave band to an infrared light wave band. Wherein, the light with the wavelength range of 780-2500nm is called near-infrared light which is used as an important component of the electromagnetic spectrum, and the near-infrared light can be widely applied to navigation, aerospace, weapon detection, night vision and other aspects in military affairs; the method can be widely applied to communication, atmospheric monitoring, pollution detection, weather and other aspects in civil use. However, the current silicon photodetectors in wide commercial use have a detection range of only 1100nm, and therefore, in order to achieve effective detection of near-infrared light exceeding 1100nm and become a potential substitute for the silicon photodetectors, the absorption spectrum of the active layer material in OPDs needs to exceed 1100 nm.
The active layer of bulk heterojunction-type OPDs is typically composed of a blend of an electron-rich p-type material and an electron-deficient n-type material. Because the n-type fullerene receptor and the derivative thereof have excellent electron transmission characteristics in the three-dimensional direction, the n-type fullerene receptor and the derivative thereof are widely used as n-type materials and various near-infrared p-type materials to be matched and applied to near-infrared organic photoelectric detectors. However, fullerene and its derivatives have the disadvantages of difficult adjustment of structure and difficult adjustment of energy level, and are difficult to realize good energy level matching with a wide variety of near-infrared donor materials, thereby resulting in poor exciton dissociation and charge collection efficiency. Finally, OPDs based on near-infrared p-type donor materials with n-type fullerene receptors tend to have poor External Quantum Efficiency (EQE), responsivity (R), and detectivity (D) (. Adv. Funct. Mater.2014,24, 7605-. For example, ZhiyuanWang et al reported in 2018 a near-infrared P-type donor material P2 with an ultra-narrow optical bandgap (adv. optical mater.2018, 1800038). With P2 and fullerene acceptor PC71The detection range of the organic photoelectric detector with BM as the active layer material exceeds 1400nm, but the application of-2V bias voltage to the device promotes exciton dissociation at the wavelength of 1100nmThe EQE response value is also only 5%, corresponding to a response of only 0.04A/W.
Therefore, it is necessary to find a technical solution to solve the technical problems in the art.
Disclosure of Invention
In recent years, n-type non-fullerene acceptor small molecules represented by ITIC and Y6 have rapidly developed, and near infrared absorption and continuously adjustable energy levels can be realized through reasonable molecular structure design. For organic semiconductors, the introduction of intrinsic quinoid units by structural design is an effective strategy to achieve near-infrared absorption. Under the driving action of aromatic stabilization energy, the intrinsic quinoid structure can remarkably improve the quinoid content in a conjugated framework, thereby reducing the optical band gap. Meanwhile, all the constituent units of the modular non-fullerene acceptor micromolecule are connected through single bonds, so that the advantages of low synthesis complexity and low cost are achieved, but no modular non-fullerene acceptor micromolecule with an absorption spectrum exceeding 1200nm is reported at present.
Therefore, the invention utilizes the advantages of the intrinsic quinoid structure that the band gap is reduced and the synthesis complexity of the modular structure is low, takes the intrinsic quinoid Q unit as a core unit, firstly invents the intrinsic quinoid near-infrared receptor micromolecules, one of which is the near-infrared modular non-fullerene receptor micromolecule BDP4Cl with A-D-Q-D-A structure, the absorption spectrum of which exceeds 1400nm, the EQE value of the photoelectric detector based on the intrinsic quinoid near-infrared receptor micromolecules is as high as 16.40 percent at 1100nm under the condition of not applying any bias voltage, and the corresponding responsivity and detectivity are respectively 0.15A/W and 7.74 multiplied by 1011Jones. And the BDP4 Cl-based detector has a large cut-off bandwidth (65kHz) and a wide linear dynamic range (70dB) for incident light of 1050nm, and a high-performance near-infrared organic photodetector is realized.
Furthermore, the invention designs and synthesizes a series of A-D-Q-D-A type near infrared small molecule receptor materials which take the intrinsic quinoid unit as the central nucleus, and the near infrared organic photoelectric detector prepared based on the A-D-Q-D-A type near infrared small molecule receptor materials also realizes the high-performance detection of near infrared light with the wavelength of more than 1100nm, which shows that the technical scheme of the invention has wide universality and feasibility.
In the comparative examples of the specific examples section of the present specification, it can be seen that the detection range of the non-fullerene acceptor small molecule DC4Cl of the A-D-D-A structure, which does not contain an intrinsic quinoid Q unit, is within 1100nm, by comparison. Further, non-fullerene acceptor small molecules DPPO4Cl and IIDCN, having similar structures A-D-A-D-A but core structures that do not form intrinsic quinoid Q units, can achieve EQE response spectra in excess of 1100nm, but only about 1% EQE response at 1100nm under 0V bias. And, despite the introduction of a strongly electron withdrawing unit BTT as a core structure, it is also possible to achieve an EQE response spectrum exceeding 1100nm, with an EQE response at 1100nm of only 2% at 0V bias.
In the above comparative examples, the core structure cannot effectively form an intrinsic quinoid structure. This shows that the introduction of the intrinsic quinoid Q unit is an effective method for inventing the high-performance near-infrared modular non-fullerene acceptor micromolecule.
The invention discloses an intrinsic quinoid near-infrared receptor micromolecule.
An intrinsic quinoid near-infrared receptor small molecule having the following structure:
Figure BDA0003469416720000021
wherein the content of the first and second substances,
n is a positive integer selected from 1 to 3;
q is a quinoid unit and Q is a quinoid unit,
d is an electron donor, A is an electron acceptor;
the quinoid unit is selected from the following structures:
Figure BDA0003469416720000031
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine, cyano and trifluoromethyl;
y is selected from any one of oxygen, sulfur and selenium;
R17-R20the radicals being selected from hydrogen, fluorine, chlorineAny one of C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl C4-C30 heteroaryl;
wherein all hydrogen atoms on said C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl or C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl or C4-C30 heteroaryl are substituted by other elements.
Further, the electron donor is selected from the following structures:
Figure BDA0003469416720000032
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R11-R16the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are substituted by other elements.
Further, the electron acceptor is selected from the following structures:
Figure BDA0003469416720000041
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R11-R16the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are substituted by other elements.
Further, n is 1.
The invention also aims to disclose a preparation method of the intrinsic quinoid near-infrared acceptor micromolecule, which comprises the following steps:
s1, reacting a monomer of a quinoid unit with a monomer of an electron donor under a catalyst to obtain an intermediate;
s2, formylating the intermediate to obtain a formylated intermediate;
and S3, reacting the formylated intermediate with a monomer of an electron acceptor, and then purifying.
Further, the molar ratio of the monomer of the quinoid unit to the monomer of the electron donor is 1:2 to 1: 3.
Further, the catalyst is selected from palladium-based catalysts.
The invention also aims to disclose the application of the intrinsic quinoid near-infrared acceptor micromolecules in an organic photoelectric detector.
Further, the intrinsic quinoid near-infrared acceptor micromolecules in the organic photoelectric detector comprise an organic compound layer, the organic compound layer comprises a photosensitive layer, and the photosensitive layer contains the intrinsic quinoid near-infrared acceptor micromolecules.
Further, the organic compound layer further includes at least one of a hole transport layer and an electron transport layer.
The invention has the beneficial effects that:
1. the structure of the intrinsic quinoid near-infrared receptor micromolecule provided by the invention can effectively improve the quinoid content of a conjugated framework and promote the delocalization of electron cloud on the conjugated framework, thereby expanding the photoresponse range to a near-infrared band; the method is applied to the field of organic photodetectors, and has high responsivity and detectivity at 1100nm, larger cut-off bandwidth and wide linear dynamic range.
2. The preparation method provided by the invention has the advantages of simple process, high yield, flexible structure adjustment, low manufacturing cost, suitability for industrial production and the like.
Drawings
FIG. 1 is a chemical structure diagram of PBT 7-Th.
FIG. 2 is a schematic structural diagram of a positive device of an organic photodetector with an active layer formed by blending near infrared acceptor small molecules and PTB 7-Th.
Fig. 3 is an EQE curve of an organic photodetector with a near-infrared acceptor small molecule blended with PTB7-Th as an active layer.
FIG. 4 is a responsivity curve of an organic photodetector with a near infrared acceptor small molecule blended with PTB7-Th as an active layer.
Fig. 5 is a dark current curve of an organic photodetector with a near-infrared acceptor small molecule blended with PTB7-Th as an active layer.
FIG. 6 is a detection rate curve of an organic photodetector with a near infrared receptor small molecule blended with PTB7-Th as an active layer.
FIG. 7 is a graph showing the cut-off bandwidths of organic photodetectors having the active layer of the near-infrared acceptor small molecules obtained in examples 1 to 3 and comparative example 4 blended with PTB 7-Th.
FIG. 8 is a graph showing the linear dynamic range of organic photodetectors having active layers obtained by blending the near-infrared receptor small molecules obtained in examples 1 to 3 and comparative example 4 with PTB 7-Th.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, but the embodiments and the protection of the invention are not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art.
The practice of the present invention may employ conventional techniques of organic chemistry within the skill of the relevant art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The temperatures used in the following examples are expressed in degrees Celsius and the pressures are at or near atmospheric. All solvents used were either analytically pure or chromatographically pure, and all reactions were carried out under an inert gas atmosphere. All reagents were obtained commercially unless otherwise indicated.
Example 1
An intrinsic quinoid near-infrared acceptor micromolecule BDP4Cl has a structural formula shown as follows:
Figure BDA0003469416720000061
the synthetic route is as follows:
Figure BDA0003469416720000062
(1) synthesis of Compound 3
Compound 1(150mg, 0.29mmol), compound 2(608mg, 0.88mmol) and palladium tetrakistriphenylphosphine (16mg, 0.0087mmol) were dissolved in a mixed solvent of 4ml toluene and 0.4ml DMF under a nitrogen atmosphere. Reflux reaction is carried out for 24h at 110 ℃, then the reaction product is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, anhydrous magnesium sulfate is used for drying, and a column chromatography separation method is adopted for separation and purification to obtain a green lacquer-like product with the yield of 70%.
(2) Synthesis of Compound 4
Ultra-dry phosphorus oxychloride (140mg, 0.91mmol) and ultra-dry DMF (209mg, 2.86mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 3(249mg, 0.22mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 75%.
(3) Synthesis of BDP4Cl
Compound 4(250mg, 0.206mmol) and compound 5(217mg, 0.826mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 90 percent.
Example 2
An intrinsic quinoid near-infrared acceptor micromolecule BDPT4NF has a structural formula shown as follows:
Figure BDA0003469416720000071
the synthetic route is as follows:
Figure BDA0003469416720000072
(1) synthesis of Compound 7
Compound 6(200mg, 0.53mmol), Compound 2(1.10g, 1.59mmol) and Tetratriphenylphosphine palladium (61mg, 0.03mmol) were dissolved in a mixed solvent of 5ml of toluene and 0.5ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying with anhydrous magnesium sulfate, and column chromatographic separation to obtain lacquer-like green product in 72% yield.
(2) Synthesis of Compound 8
Ultra-dry phosphorus oxychloride (233mg, 1.52mmol) and ultra-dry DMF (361mg, 4.94mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask, compound 7(389mg, 0.38mmol) dissolved in 10ml of ultra-dry 1, 2-dichloroethane was added dropwise. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 80%.
(3) Synthesis of BDPT4NF
Compound 8(327mg, 0.30mmol) and compound 9(252mg, 0.90mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 90 percent.
Example 3
An intrinsic quinoid near-infrared acceptor micromolecule BPDO4Cl, which has the structural formula shown as follows:
Figure BDA0003469416720000081
the synthetic route is as follows:
Figure BDA0003469416720000082
(1) synthesis of Compound 12
Compound 10(300mg, 0.45mmol), compound 11(954mg, 1.35mmol) and palladium tetrakistriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction is carried out for 24h at 110 ℃, then the reaction product is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, anhydrous magnesium sulfate is used for drying, and a column chromatography separation method is adopted for separation and purification to obtain a green lacquer-like product with the yield of 65%.
(2) Synthesis of Compound 13
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. Compound 12(386mg, 0.29mmol) dissolved in 8ml of ultra dry 1, 2-dichloroethane is added dropwise to the reaction flask. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 78%.
(3) Synthesis of BPDO4Cl
Compound 13(319mg, 0.23mmol) and compound 5(201mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 90 percent.
Example 4
An intrinsic quinoid near-infrared acceptor micromolecule BDPO4Cl has a structural formula shown as follows:
Figure BDA0003469416720000091
the synthetic route is as follows:
Figure BDA0003469416720000101
(1) synthesis of Compound 14
Compound 1(230mg, 0.45mmol), compound 11(954mg, 1.35mmol) and palladium tetratriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction is carried out for 24h at 110 ℃, then the reaction product is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, anhydrous magnesium sulfate is used for drying, and a column chromatography separation method is adopted for separation and purification to obtain a green lacquer-like product with the yield of 60%.
(2) Synthesis of Compound 15
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. Compound 14(356mg, 0.30mmol) dissolved in 8ml of ultra dry 1, 2-dichloroethane was added dropwise to the reaction flask. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 82%.
(3) Synthesis of BDPO4Cl
Compound 15(248mg, 0.20mmol) and compound 5(210mg, 0.80mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 91%.
Example 5
An intrinsic quinoid near-infrared receptor small molecule BDTDO4Cl, which has the following structural formula:
Figure BDA0003469416720000111
the synthetic route is as follows:
Figure BDA0003469416720000112
(1) synthesis of Compound 16
Compound 6(170mg, 0.45mmol), compound 11(954mg, 1.35mmol) and palladium tetratriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying with anhydrous magnesium sulfate, and column chromatographic separation to obtain true lacquer product in 55% yield.
(2) Synthesis of Compound 17
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 16(305mg, 0.29mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 75%.
(3) Synthesis of BDTDO4Cl
Compound 17(255mg, 0.23mmol) and compound 5(242mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 93 percent.
Example 6
An eigen-quinoid near-infrared acceptor micromolecule TQTP2F has a structural formula shown as follows:
Figure BDA0003469416720000121
the synthetic route is as follows:
Figure BDA0003469416720000122
(1) synthesis of Compound 20
Compound 18(308mg, 0.45mmol), compound 19(783mg, 1.35mmol) and palladium tetratriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction is carried out for 24h at 110 ℃, then the reaction product is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, anhydrous magnesium sulfate is used for drying, and a column chromatography separation method is adopted for separation and purification to obtain a green lacquer-like product, wherein the yield is 66%.
(2) Synthesis of Compound 21
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 20(285mg, 0.29mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 88%.
(3) Synthesis of TQTP2F
Compound 21(253mg, 0.23mmol) and compound 22(211mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 88 percent.
Example 7
An intrinsic quinoid near-infrared acceptor micromolecule TQFCN has the following structural formula:
Figure BDA0003469416720000131
the synthetic route is as follows:
Figure BDA0003469416720000132
(1) synthesis of Compound 24
Compound 18(308mg, 0.45mmol), compound 23(1406mg, 1.35mmol) and palladium tetrakistriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction is carried out for 24h at 110 ℃, then the reaction product is cooled to room temperature, dichloromethane is used for extraction, an organic phase is washed by saturated saline solution, anhydrous magnesium sulfate is used for drying, and a column chromatography separation method is adopted for separation and purification to obtain a green lacquer-like product with the yield of 75%.
(2) Synthesis of Compound 25
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 24(394mg, 0.29mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 75%.
(3) Synthesis of TQFCN
Compound 25(325mg, 0.23mmol) and compound 26(201mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 92 percent.
Example 8
An intrinsic quinoid near-infrared receptor micromolecule IIDTCN, which has the following structural formula:
Figure BDA0003469416720000141
the synthetic route is as follows:
Figure BDA0003469416720000142
(1) synthesis of Compound 28
Compound 27(293mg, 0.45mmol), Compound 2(932mg, 1.35mmol) and Tetratriphenylphosphine palladium (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying with anhydrous magnesium sulfate, and column chromatographic separation to obtain green lacquer-like product in 70% yield.
(2) Synthesis of Compound 29
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. Compound 28(375mg, 0.29mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane was added dropwise to the reaction flask. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 79%.
(3) Synthesis of IIDTCN
Compound 29(311mg, 0.23mmol) and compound 26(201mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of super-dry pyridine was added and reacted at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 88 percent.
Example 9
An intrinsic quinoid near-infrared acceptor micromolecule IIDTN2F, which has the following structural formula:
Figure BDA0003469416720000151
the synthetic route is as follows:
Figure BDA0003469416720000161
(1) synthesis of Compound 30
Compound 27(293mg, 0.45mmol), compound 19(783mg, 1.35mmol) and palladium tetratriphenylphosphine (55mg, 0.03mmol) were dissolved in a mixed solvent of 6ml of toluene and 0.6ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying with anhydrous magnesium sulfate, and column chromatographic separation to obtain lacquer-like green product in 53% yield.
(2) Synthesis of Compound 31
Ultra-dry phosphorus oxychloride (178mg, 1.16mmol) and ultra-dry DMF (275mg, 3.77mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 30(327mg, 0.29mmol) dissolved in 8ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain blue lacquer-like product with yield of 74%.
(3) Synthesis of IIDTN2F
Compound 31(260mg, 0.23mmol) and compound 9(257mg, 0.92mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, 1.3ml of super-dry pyridine was added, and reaction was carried out at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 93 percent.
Comparative example 1
A small acceptor molecule DC4Cl containing no intrinsic quinoid unit has a structural formula shown as follows:
Figure BDA0003469416720000171
the synthetic route is as follows:
Figure BDA0003469416720000172
(1) synthesis of Compound 33
Under a nitrogen atmosphere, compound 32(800mg, 1.86mmol), PdCl2(PhCN)2(22mg, 0.056mmol), potassium fluoride (216mg, 3.72mmol) and silver nitrate (632mg, 3.72mmol) were dissolved in 6ml of ultra-dry DMSO and stirred at 60 ℃ overnight. Cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated brine, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain red solid product with high yield60％。
(2) Synthesis of DC4Cl
Compound 33(300mg, 0.35mmol) and compound 5(367mg, 1.4mmol) were dissolved in 15ml of chloroform under a nitrogen atmosphere, and 1.5ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. Separating and purifying by column chromatography to obtain blue-black solid product with metallic luster, with yield of 90%.
Comparative example 2
A near-infrared acceptor micromolecule DPPO4Cl not containing an intrinsic quinoid structure has a structural formula shown as follows:
Figure BDA0003469416720000173
the synthetic route is as follows:
Figure BDA0003469416720000181
(1) synthesis of Compound 35
Ultra-dry phosphorus oxychloride (140mg, 0.91mmol) and ultra-dry DMF (209mg, 2.86mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 34(262mg, 0.22mmol) dissolved in 6ml of ultra dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain the product with yield of 75%.
(2) Synthesis of DPPO4Cl
Compound 35(257mg, 0.206mmol) and compound 5(217mg, 0.826mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 90 percent.
Comparative example 3
A near-infrared acceptor micromolecule IIDCN without an intrinsic quinoid structure has a structural formula shown as follows:
Figure BDA0003469416720000182
the synthetic route is as follows:
Figure BDA0003469416720000191
(1) synthesis of Compound 37
Compound 36(170mg, 0.29mmol), Compound 2(608mg, 0.88mmol) and Tetratriphenylphosphine palladium (16mg, 0.0087mmol) were dissolved in a mixed solvent of 4ml of toluene and 0.4ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying over anhydrous magnesium sulfate, and column chromatographic separation to obtain the product in 68% yield.
(2) Synthesis of Compound 38
Ultra-dry phosphorus oxychloride (140mg, 0.91mmol) and ultra-dry DMF (209mg, 2.86mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 37(270mg, 0.22mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain the product with yield of 80%.
(3) Synthesis of IIDCN
Compound 38(260mg, 0.206mmol) and compound 22(190mg, 0.826mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 91%.
Comparative example 4
A near-infrared acceptor micromolecule BTTCIC-4F without an intrinsic quinoid structure has a structural formula shown as follows:
Figure BDA0003469416720000201
the synthetic route is as follows:
Figure BDA0003469416720000202
(1) synthesis of Compound 40
Compound 39(102mg, 0.29mmol), Compound 2(608mg, 0.88mmol) and Tetratriphenylphosphine palladium (16mg, 0.0087mmol) were dissolved in a mixed solvent of 4ml of toluene and 0.4ml of DMF under a nitrogen atmosphere. Reflux reaction at 110 deg.c for 24 hr, cooling to room temperature, extraction with dichloromethane, washing the organic phase with saturated salt solution, drying over anhydrous magnesium sulfate, and column chromatographic separation to obtain 73% yield.
(2) Synthesis of Compound 41
Ultra-dry phosphorus oxychloride (140mg, 0.91mmol) and ultra-dry DMF (209mg, 2.86mmol) were stirred at 0 ℃ for 30min under a nitrogen atmosphere. To the reaction flask was added dropwise compound 40(219mg, 0.22mmol) dissolved in 6ml of ultra-dry 1, 2-dichloroethane. The temperature is increased to 90 ℃ for reaction for 12 h. Adding saturated sodium bicarbonate water solution, stirring for 2 hr, cooling to room temperature, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography to obtain the product with yield of 80%.
(3) Synthesis of BTTCIC-4F
Compound 41(216mg, 0.206mmol) and compound 22(190mg, 0.826mmol) were dissolved in 13ml of chloroform under a nitrogen atmosphere, and 1.3ml of ultra-dry pyridine was added to react at 65 ℃ for 1 hour. The reaction solution was concentrated and settled in 200ml of anhydrous methanol, and a crude product solid was obtained by suction filtration. The black solid product with metallic luster is obtained by separation and purification by adopting a column chromatography separation method, and the yield is 91%.
Test example
Test example 1
All the near-infrared acceptor small molecules obtained in the above examples and comparative examples are taken as examples to illustrate the application of the near-infrared acceptor small molecules in a near-infrared organic photodetector.
The specific preparation process of each near-infrared organic photoelectric detector is as follows:
and (3) spinning a 40nm PEDOT (polymer ethylene terephthalate) (PSS) hole transport layer on ITO (indium tin oxide), respectively spinning a polymer donor PTB7-Th with the blended photoactive layer of the near-infrared acceptor micromolecules obtained in each embodiment or comparative example, spinning a quaternary ammonium bromide salt (PFN-Br) of amino polyfluorene with the thickness of about 5nm as a cathode interface layer, and evaporating a 100nm Ag layer to finish the preparation of the device. The structural formula of PTB7-Th is shown in figure 1.
The organic photoelectric detector comprises a transparent conductive anode, an anode interface layer, a polymer donor/small molecule acceptor active layer, a cathode interface layer and a cathode from bottom to top in sequence. The resulting device structure is shown in fig. 2. EQE and dark current measurements were performed on the above organic photodetector under 0V bias and the corresponding responsivity R and detectivity D were calculated, the specific performance parameters are shown in table 1. Wherein, the responsivity R refers to the ratio of the photocurrent of the photoelectric detector to the incident light intensity, the unit is A/W, and the calculation formula of R is as follows:
Figure BDA0003469416720000211
where EQE is in direct proportion to R, both of which reflect the efficiency of photon to electron conversion. The detectivity D, defined as the inverse of the Noise Equivalent Power (NEP), is an indicator of the ability of the detector to detect the minimum incident optical signal, and is calculated in units of Jones, D as follows:
Figure BDA0003469416720000212
wherein R isResponsivity, q is the charge, JdIs a dark current.
FIGS. 3-6 show EQE of several positive organic photoelectric detectors obtained by using all the near infrared acceptor small molecules obtained in examples and comparative examples as acceptor materials and PTB7-Th as donor materials.
FIGS. 7-8 show the responsivity of several positive organic photoelectric detectors obtained by using all the near infrared acceptor small molecules obtained in the examples and comparative examples as acceptor materials and PTB7-Th as donor materials. The resulting device data are shown in table 1.
TABLE 1 testing example 1 device parameters at 1100nm for an organic photodetector with a near infrared receptor small molecule PTB7-Th as the active layer at 0V bias
Figure BDA0003469416720000213
Figure BDA0003469416720000221
Table 2 shows the application of the near-infrared acceptor small molecules of the specific examples and comparative examples to the response parameters of the organic photodetector to the 1050nm LED.
Table 2 test example 1 shows that the response parameter of an organic photodetector with a near infrared receptor small molecule PTB7-Th as an active layer under 0V bias to 1050nm LED
Figure BDA0003469416720000222
The above data demonstrate that the detection range of non-fullerene acceptor small molecules of the A-D-D-A structure without intrinsic quinoid Q units is within 1100 nm. While non-fullerene acceptor small molecules with similar structures A-D-A-D-A but with core structures that do not form intrinsic quinoid Q units can achieve EQE response spectra over 1100nm, the EQE response at 1100nm is only about 1% at 0V bias. And the non-fullerene acceptor small molecule based on the intrinsic quinoid Q unit can realize more than 16% of high EQE response at 1100nm, which shows that the introduction of the intrinsic quinoid Q unit is an effective method for inventing the high-performance near-infrared modular non-fullerene acceptor small molecule.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. An intrinsic quinoid near-infrared receptor small molecule, characterized in that the intrinsic quinoid near-infrared receptor small molecule has the following structure:
Figure FDA0003469416710000011
wherein the content of the first and second substances,
n is a positive integer selected from 1 to 3;
q is a quinoid unit and Q is a quinoid unit,
d is an electron donor, A is an electron acceptor;
the quinoid unit is selected from the following structures:
Figure FDA0003469416710000012
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine, cyano and trifluoromethyl;
y is selected from any one of oxygen, sulfur and selenium;
R17-R20the group is any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl C4-C30 heteroaryl;
wherein all hydrogen atoms on said C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester, C6-C30 aryl or C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl or C4-C30 heteroaryl are substituted by other elements.
2. The intrinsic quinoid near-infrared acceptor small molecule according to claim 1, wherein said electron donor is selected from the following structures:
Figure FDA0003469416710000021
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R11-R16the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are substituted by other elements.
3. The intrinsic quinoid near-infrared acceptor small molecule according to claim 1, wherein said electron acceptor is selected from the following structures:
Figure FDA0003469416710000022
wherein, X is selected from any one of fluorine, chlorine, bromine, iodine and cyano;
y is selected from any one of oxygen, sulfur and selenium;
z is selected from any one of carbon, silicon and germanium;
R11-R16the group is selected from any one of hydrogen, fluorine atom, chlorine atom, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl;
wherein all hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are unsubstituted,
or one or more hydrogen atoms on the C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 ester group, C6-C30 aryl and C4-C30 heteroaryl are substituted by other elements.
4. The intrinsic quinoid near-infrared receptor small molecule according to claim 1, wherein n is 1.
5. A process for the preparation of a small molecule of an intrinsic quinoid near-infrared receptor according to any one of claims 1 to 4, comprising the steps of:
s1, reacting a monomer of a quinoid unit with a monomer of an electron donor under a catalyst to obtain an intermediate;
s2, formylating the intermediate to obtain a formylated intermediate;
and S3, reacting the formylated intermediate with a monomer of an electron acceptor, and then purifying.
6. The method for preparing the intrinsic quinoid near-infrared acceptor micromolecule according to claim 5, wherein the molar ratio of the monomer of the quinoid unit to the monomer of the electron donor is 1:2-1: 3.
7. The method of claim 5, wherein the catalyst is selected from palladium-based catalysts.
8. Use of the small intrinsic quinoid near-infrared receptor molecule of any one of claims 1 to 4 in an organic photodetector.
9. The intrinsic quinoid near-infrared acceptor small molecule according to claim 8, wherein said intrinsic quinoid near-infrared acceptor small molecule in organic photodetector comprises an organic compound layer, said organic compound layer comprises a photosensitive layer, said photosensitive layer contains intrinsic quinoid near-infrared acceptor small molecule.
10. The intrinsic quinoid near-infrared acceptor small molecule-based organic photodetector as claimed in claim 9, wherein said organic compound layer further comprises at least one of a hole transport layer and an electron transport layer.
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